Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
  • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2420/00—Metallocene catalysts
  • C08F2420/02—Cp or analog bridged to a non-Cp X anionic donor
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
  • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+

Definitions

• the present invention relates to a method for producing a cyclic olefin copolymer.
• Cyclic olefin polymers and cyclic olefin copolymers (also called “COP” and “COC”, respectively) have low moisture absorption and high transparency. For this reason, COPs and COCs are used in various applications, including optical materials such as optical disk substrates, optical films, and optical fibers.
• a representative COC is a copolymer of cyclic olefin and ethylene. The glass transition temperature (Tg) of such a copolymer can be changed by the copolymerization composition of the cyclic olefin and ethylene.
• a copolymer of cyclic olefin and ethylene can be manufactured as a copolymer with a higher Tg than COP, and it is possible to achieve a Tg of over 200°C, which is difficult with COP.
• such copolymers are hard and brittle. For this reason, such copolymers have problems such as low mechanical strength and poor handling and processability.
• One method for improving the mechanical strength of high TgCOC is to copolymerize cyclic olefins with ⁇ -olefins other than ethylene (hereinafter referred to as "specific ⁇ -olefins").
• specific ⁇ -olefins cyclic olefins other than ethylene
• copolymerization of cyclic olefins and specific ⁇ -olefins is significantly different from the copolymerization of cyclic olefins and ethylene.
• chain transfer reactions caused by the specific ⁇ -olefins occur in the copolymerization of cyclic olefins and specific ⁇ -olefins, making it difficult to obtain high molecular weight materials.
• copolymers of cyclic olefins and specific ⁇ -olefins have been considered unsuitable for use as molding materials (see, for example, Non-Patent Document 1).
• the present invention was made in consideration of the above circumstances, and aims to provide a method for efficiently producing a cyclic olefin copolymer, which is a copolymer of a cyclic olefin monomer and an ⁇ -olefin having 3 to 20 carbon atoms and has excellent toughness.
• the present inventors have found that the above problems can be solved by producing a copolymer of a cyclic olefin monomer and an ⁇ -olefin having 3 to 20 carbon atoms by a method including: a first polymerization in which a cyclic olefin monomer and a monomer including an ⁇ -olefin are polymerized in a polymerization vessel in the presence of a titanocene catalyst, an alkylaluminum compound, and a borate compound; adding an alkylaluminum compound alone to the polymerization vessel after the first polymerization; and a second polymerization in which, after the addition of the alkylaluminum compound, a monomer is added to the polymerization vessel and the monomer is continuously polymerized, thereby completing the present invention. More specifically, the present invention provides the following.
• a method for producing a cyclic olefin copolymer having a unit derived from a cyclic olefin monomer and a unit derived from an ⁇ -olefin having 3 to 20 carbon atoms comprising the steps of: The above manufacturing method a first polymerization step of polymerizing a cyclic olefin monomer and a monomer containing an ⁇ -olefin in the presence of a titanocene catalyst, an alkylaluminum compound, and a borate compound in a polymerization vessel; adding an alkylaluminum compound alone into the polymerization vessel after the first polymerization; a second polymerization step of adding monomer into the polymerization vessel after the addition of the alkylaluminum compound and subsequently polymerizing the monomer; A method for producing a cyclic olefin copolymer, wherein in the first polymerization, polymerization of the monomer is carried out until a reaction rate of the
• (V) A method for producing a cyclic olefin copolymer according to (VI), in which in the first polymerization and/or the second polymerization, the monomer is added in two batches to the polymerization vessel.
• (X) A method for producing a cyclic olefin copolymer according to any one of (I) to (IX), in which the alkylaluminum compound used in the first polymerization is a long-chain alkylaluminum compound having only alkyl groups with 6 or more carbon atoms, and the alkylaluminum compound added to the polymerization vessel after the first polymerization is a short-chain alkylaluminum compound having only alkyl groups with 5 or less carbon atoms.
• both an alkylaluminum compound I and an alkylaluminum compound II different from the alkylaluminum compound I are used as alkylaluminum compounds,
• the alkylaluminum compound I has at least one alkyl group having 6 or more carbon atoms
• (XII) The method for producing a cyclic olefin copolymer described in (X), wherein the alkylaluminum compound is at least one selected from the group consisting of trimethylaluminum, triethylaluminum, triisobutylaluminum, and trioctylaluminum.
• the alkylaluminum compound I is trioctylaluminum, The method for producing a cyclic olefin copolymer according to (XI), wherein the alkylaluminum compound II is trimethylaluminum, triethylaluminum, or triisobutylaluminum.
• (XIV) A method for producing a cyclic olefin copolymer according to any one of (X) to (XIII), in which the amount of the cyclic olefin copolymer obtained is 200 g or more per 1 g of titanocene catalyst, and the number average molecular weight of the cyclic olefin copolymer obtained is 10,000 to 100,000.
• the titanocene catalyst is represented by the following formula (1):
• R 1 to R 3 are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms
• R 4 and R 5 are each independently an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a halogen atom
• R 6 to R 13 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a silyl group which may have a monovalent hydrocarbon group having 1 to 12 carbon atoms as a substituent.
• (XVI) A method for producing a cyclic olefin copolymer according to any one of (1) to (XV), wherein the cyclic olefin copolymer has two or more glass transition temperatures within the range of 0 to 300°C.
• the present invention provides a method for efficiently producing a cyclic olefin copolymer, which is a copolymer of a cyclic olefin monomer and an ⁇ -olefin having 3 to 20 carbon atoms and has excellent toughness.
• the cyclic olefin copolymer produced by the production method described below is an addition type polymer of a cyclic olefin monomer and an ⁇ -olefin having 3 to 20 carbon atoms.
• the ratio of the number of moles of structural units derived from ⁇ -olefin to the number of moles of all structural units in the cyclic olefin copolymer is not particularly limited, and is preferably 10 to 50 mol%, more preferably 20 to 40 mol%, and even more preferably 20 to 30 mol%.
• the cyclic olefin copolymer has structural units derived from ⁇ -olefin in the above ratio, the cyclic olefin copolymer has high tensile strength and tensile modulus, a high glass transition temperature, and excellent heat resistance.
• the ratio of the number of moles of structural units derived from ⁇ -olefin can be calculated by measuring 13 C-NMR spectrum.
• the cyclic olefin copolymer may contain structural units other than the structural units derived from the cyclic olefin monomer and the structural units derived from the ⁇ -olefin having 3 to 20 carbon atoms, to the extent that the object of the present invention is not hindered.
• structural units derived from a compound that is copolymerizable with the cyclic olefin monomer and the ⁇ -olefin having 3 to 20 carbon atoms and has a carbon-carbon unsaturated double bond may be used.
• structural units derived from ethylene are preferred as the other structural units.
• the sum of the ratio of the number of moles of structural units derived from cyclic olefin monomers and the ratio of the number of moles of structural units derived from ⁇ -olefins to the number of moles of all structural units is preferably 80 mol% or more, more preferably 90 mol% or more, even more preferably 95 mol% or more, and most preferably 100 mol%.
• the cyclic olefin copolymer preferably has two or more glass transition temperatures within the range of 0 to 300°C.
• the glass transition temperature can be measured by using a film-like molded product having a thickness of 50 ⁇ m and observing the viscoelastic behavior with a solid rheometer at ⁇ 100 to 300° C. Specifically, the glass transition temperature is determined as the peak top temperature of the peak in the tan ⁇ chart obtained by the above-mentioned measurement.
• the cyclic olefin copolymer has at least one glass transition temperature in the range of 0 to 100°C and at least one glass transition temperature in the range of 160 to 300°C.
• the cyclic olefin copolymer preferably has at least one glass transition temperature each in the range of less than 0° C., in the range of 0 to 100° C., and in the range of 160 to 300° C., since the breaking strain measured by a tensile test is large and the toughness is excellent.
• the range of 30 to 80°C is preferred, and the range of 50 to 80°C is more preferred.
• the cyclic olefin copolymer has one glass transition temperature each in the range of 0 to 100°C and in the range of 160 to 300°C, or it is preferable that the cyclic olefin copolymer has one glass transition temperature each in the range below 0°C, the range of 0 to 100°C, and the range of 160 to 300°C.
• the molecular weight of the cyclic olefin copolymer is not particularly limited.
• the weight average molecular weight (Mw) of the cyclic olefin copolymer is preferably 5,000 to 200,000, more preferably 10,000 to 100,000, in terms of polystyrene measured by gel permeation chromatography (GPC).
• the number average molecular weight (Mn) of the cyclic olefin copolymer is preferably 5,000 to 200,000, and more preferably 10,000 to 100,000, in terms of polystyrene, measured by gel permeation chromatography (GPC).
• the dispersity ratio (Mw/Mn) is not excessively high. Specifically, the dispersity ratio (Mw/Mn) is preferably 1.85 or less, more preferably 1.75 or less, and even more preferably 1.70 or less.
• the lower limit of the polydispersity ratio (Mw/Mn) is not particularly limited.
• the polydispersity ratio (Mw/Mn) may be, for example, 1.1 or more.
• the cyclic olefin monomer is not particularly limited as long as it does not impair the object of the present invention.
• norbornene and substituted norbornene are preferably used as the cyclic olefin monomer.
• Norbornene is particularly preferred as the cyclic olefin monomer, in terms of the good balance of cost, polymerizability, and physical properties of the resulting cyclic olefin copolymer.
• the cyclic olefin monomer can be used alone or in combination of two or more.
• the substituted norbornene is not particularly limited.
• substituents that the substituted norbornene has include halogen atoms and monovalent or divalent hydrocarbon groups.
• Specific examples of the substituted norbornene include the compound represented by the following formula (I).
• R a1 to R a12 may be the same or different and each represents an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group.
• R a9 and R a10 , and R a11 and R 12 may combine together to form a divalent hydrocarbon group.
• R a9 or R a10 and R a11 or R a12 may be bonded to each other to form a ring.
• n is 0 or a positive integer. When n is 2 or more, R a5 to R a8 may be the same or different in each repeating unit. However, when n is 0, at least one of R a1 to R a4 and R a9 to R a12 is not a hydrogen atom.
• R a1 to R a8 include a hydrogen atom, a halogen atom such as fluorine, chlorine, and bromine, and an alkyl group having 1 to 20 carbon atoms.
• R a1 to R a8 may all be different atoms or groups. Some or all of R a1 to R a8 may be the same atom or group.
• R a9 to R a12 include a hydrogen atom; a halogen atom such as fluorine, chlorine, and bromine; an alkyl group having 1 to 20 carbon atoms; a cycloalkyl group such as a cyclohexyl group; a substituted or unsubstituted aromatic hydrocarbon group such as a phenyl group, a tolyl group, an ethylphenyl group, an isopropylphenyl group, a naphthyl group, and an anthryl group; and an aralkyl group such as a benzyl group and a phenethyl group. All of R a9 to R a12 may be different atoms or groups. Some or all of R a9 to R a12 may be the same atom or group.
• divalent hydrocarbon group that can be formed by combining R a9 and R a10 , or R a11 and R a12 together, include alkylidene groups such as an ethylidene group, a propylidene group, and an isopropylidene group.
• the ring formed may be a monocyclic ring or a polycyclic ring.
• the ring formed may be a polycyclic ring having a bridge.
• the ring formed may have a double bond.
• the ring formed may have a substituent such as a methyl group.
• substituted norbornene represented by formula (I) include 5-methyl-bicyclo[2.2.1]hept-2-ene, 5,5-dimethyl-bicyclo[2.2.1]hept-2-ene, 5-ethyl-bicyclo[2.2.1]hept-2-ene, 5-butyl-bicyclo[2.2.1]hept-2-ene, 5-ethylidene-bicyclo[2.2.1]hept-2-ene, 5-hexyl-bicyclo[2.2.1]hept-2-ene, 5-methyl-bicyclo[2.2.1]hept-2-ene, 5,5-dimethyl-bicyclo[2.2.1]hept-2-ene, 5-ethylidene-bicyclo[2.2.1]hept-2-ene, 5-hexyl ...
• Bicyclic olefins such as cyclo[2.2.1]hept-2-ene, 5-octyl-bicyclo[2.2.1]hept-2-ene, 5-octadecyl-bicyclo[2.2.1]hept-2-ene, 5-methylidene-bicyclo[2.2.1]hept-2-ene, 5-vinyl-bicyclo[2.2.1]hept-2-ene, and 5-propenyl-bicyclo[2.2.1]hept-2-ene; Tricyclo[4.3.0.1 2,5 ]deca-3,7-diene (common name: dicyclopentadiene), tricyclo[4.3.0.1 2,5 ]deca-3-ene; tricyclo[4.4.0.1 2,5 ]undeca-3,7-diene or tricyclo[4.4.0.1 2,5 ]undeca-3,8-diene, or their partial hydrogenated products (or adducts of cyclopentadiene and cyclohexene), tricycl
• alkyl-substituted norbornenes such as bicyclo[2.2.1]hept-2-ene substituted with one or more alkyl groups
• alkylidene-substituted norbornenes such as bicyclo[2.2.1]hept-2-ene substituted with one or more alkylidene groups
• 5-ethylidene-bicyclo[2.2.1]hept-2-ene commonly name: 5-ethylidene-2-norbornene, or simply ethylidenenorbornene
• the ⁇ -olefin is an ⁇ -olefin having from 3 to 20 carbon atoms.
• an ⁇ -olefin not only an unsubstituted ⁇ -olefin but also a substituted ⁇ -olefin having a substituent such as a halogen atom can be used.
• the number of carbon atoms in the ⁇ -olefin is 3 to 20, preferably 4 to 12, and more preferably 6 to 10.
• ⁇ -olefins having 3 to 12 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, and 1-dodecene.
• 1-hexene, 1-octene, and 1-decene are preferred, and 1-hexene and 1-octene are more preferred.
• the above cyclic olefin copolymers can be mixed with various additives as necessary, and then molded into, for example, a film or sheet, and used widely in a variety of applications, such as packaging and optical applications.
• Additives that can be added to the cyclic olefin copolymer include antioxidants, weather stabilizers, ultraviolet absorbers, antibacterial agents, flame retardants, colorants, etc. These additives are added to the cyclic olefin copolymer in amounts that take into account the typical usage amounts for each type of additive.
• the method for producing a cyclic olefin copolymer described below produces a cyclic olefin copolymer having units derived from a cyclic olefin monomer and units derived from an ⁇ -olefin having 3 to 20 carbon atoms.
• the cyclic olefin copolymer is as described above.
• the above manufacturing method is a first polymerization step of polymerizing a cyclic olefin monomer and a monomer containing an ⁇ -olefin in the presence of a titanocene catalyst, an alkylaluminum compound, and a borate compound in a polymerization vessel; adding an alkylaluminum compound alone into the polymerization vessel after the first polymerization; and a second polymerization step of adding monomer into the polymerization vessel after the addition of the alkylaluminum compound and subsequently polymerizing the monomer.
• polymerization of the monomer is carried out until the reaction rate of the cyclic olefin monomer becomes 80 mol % or more based on the total number of moles of the cyclic olefin monomer added to the polymerization vessel at the start of the first polymerization and during the first polymerization.
• the above method makes it possible to efficiently produce a cyclic olefin copolymer that is a copolymer of a cyclic olefin monomer and an ⁇ -olefin having 3 to 20 carbon atoms and has excellent toughness.
• the first polymerization, addition of the alkylaluminum compound, and the second polymerization are described below.
• a cyclic olefin monomer and a monomer containing an ⁇ -olefin are polymerized in a polymerization vessel in the presence of a titanocene catalyst, an alkylaluminum compound, and a borate compound.
• polymerization of the monomer is carried out until the reaction rate of the cyclic olefin monomer becomes 80 mol % or more based on the total number of moles of the cyclic olefin monomer added to the polymerization vessel at the start of the first polymerization and during the first polymerization.
• a cyclic olefin copolymer having at least one glass transition temperature each in the range of less than 0° C., the range of 0 to 100° C., and the range of 160 to 300° C. and excellent toughness.
• the cyclic olefin monomer and the monomer containing an ⁇ -olefin are as described above.
• monomers are added to a polymerization vessel in both the first polymerization and the second polymerization.
• the total amount of monomers added to the polymerization vessel in the first polymerization is preferably 20 to 80 mol %, more preferably 30 to 70 mol %, and even more preferably 40 to 60 mol %, based on the total moles of monomers used in the production of the cyclic olefin copolymer.
• the monomer may be added to the polymerization vessel in a plurality of portions.
• the number of times of addition of the monomer during the first polymerization is not particularly limited, but is preferably 1 to 5 times, more preferably 1 to 3 times, and even more preferably 1 or 2 times.
• the amount of the monomer added per portion is preferably TA/N ⁇ 0.5 to TA/N ⁇ 1.5, more preferably TA/N ⁇ 0.7 to TA/N ⁇ 1.3, and even more preferably TA/N ⁇ 0.9 to TA/N ⁇ 1.1, where TA is the total mole number of the monomer added in the first polymerization and N is the number of portions.
• the time from the time when the monomer is added in any one of the multiple additions to the time when the next monomer is added is preferably TT/N x 0.5 to TT/N x 1.5, more preferably TT/N x 0.7 to TT/N x 1.3, and even more preferably TT/N x 0.9 to TT/N x 1.1, where TT is the total time of the first polymerization and N is the number of additions.
• the titanocene catalyst is not particularly limited as long as it is a titanocene catalyst capable of copolymerizing a cyclic olefin monomer and an ⁇ -olefin having 3 to 20 carbon atoms.
• the titanocene catalyst is appropriately selected from known titanocene catalysts capable of copolymerizing a cyclic olefin monomer and an ⁇ -olefin having 3 to 20 carbon atoms.
• the titanocene catalyst may be used alone or in combination of two or more kinds.
• a preferred titanocene catalyst is represented by the following formula (1): (In formula (1), R 1 to R 3 are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms; R 4 and R 5 are each independently an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a halogen atom; and R 6 to R 13 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a silyl group which may have a monovalent hydrocarbon group having 1 to 12 carbon atoms as a substituent.)
• R 1 to R 3 are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms. Specific examples thereof include alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, a cyclopentyl group, and a cyclohexyl group; and aryl groups such as a phenyl group, a biphenyl group, a phenyl group or a biphenyl group having the above-mentioned alkyl group as a substituent, a naphthyl group, and a naphthyl group having the above-mentioned alkyl group as a substituent.
• alkyl groups such as a methyl group, an ethyl group,
• R4 and R5 are each independently an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a halogen atom. Specific examples thereof include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, or any of these alkyl groups having the above-mentioned halogen atom as a substituent; a phenyl group, a biphenyl group, a naphthyl group, or any of these
• R 6 to R 13 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a silyl group which may have a monovalent hydrocarbon group having 1 to 12 carbon atoms as a substituent.
• alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a cyclopentyl group, and a cyclohexyl group.
• aryl group having 6 to 12 carbon atoms include a phenyl group, a biphenyl group, a naphthyl group, and these aryl groups having the above alkyl group as a substituent.
• silyl group having a monovalent hydrocarbon group having 1 to 12 carbon atoms as a substituent examples include silyl groups having an alkyl group having 1 to 12 carbon atoms as a substituent, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a cyclopentyl group, or a cyclohexyl group.
• titanocene catalyst represented by the general formula (1) examples include (isopropylamido)dimethyl-9-fluorenylsilane titanium dimethyl, (isobutylamido)dimethyl-9-fluorenylsilane titanium dimethyl, (t-butylamido)dimethyl-9-fluorenylsilane titanium dimethyl, (isopropylamido)dimethyl-9-fluorenylsilane titanium dichloride, (isobutylamido)dimethyl-9-(3,6-dimethylfluorenyl)silane titanium dichloride, (t-butylamido)dimethyl-9-fluorenylsilane titanium dichloride, (isopropylamido)dimethyl-9-(3,6-dimethylfluorenyl)silanetitanium dichloride, (isobutylamido)dimethyl-9-(3,6-dimethylfluorenyl)silanetitanium dich
• (t-butylamido)dimethyl-9-fluorenylsilane titanium dimethyl (t-BuNSiMe 2 Flu)TiMe 2 ).
• (t-BuNSiMe 2 Flu)TiMe 2 is a titanium complex represented by the following formula (2), and can be easily synthesized, for example, based on the description in "Macromolecules, Vol. 31, p. 3184, 1998.”
• Me represents a methyl group
• t-Bu represents a tert-butyl group
• the amount of the titanocene catalyst used is not particularly limited as long as the addition polymerization reaction proceeds well.
• the amount of the titanocene catalyst used is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, and even more preferably 0.1 to 1 part by mass, per 100 parts by mass of the total amount of the cyclic olefin monomer and the ⁇ -olefin.
• the titanocene catalyst may be added to the polymerization vessel after the initiation of the first polymerization, other than at the initiation of the first polymerization. However, it is preferred that the entire amount of the titanocene catalyst used to produce the cyclic olefin copolymer is charged to the polymerization vessel at the initiation of the first polymerization.
• Alkyl aluminum compounds The first polymerization is carried out in the presence of a titanocene catalyst, an alkylaluminum compound, and a borate compound.
• the alkylaluminum compound which is charged to the polymerization vessel at the start of the polymerization acts as a scavenger to capture water, oxygen, and other impurities.
• the alkylaluminum compound charged into the polymerization vessel at the start of polymerization can be any alkylaluminum compound that has been used conventionally in the homopolymerization or copolymerization of cyclic olefin monomers, without any particular limitation.
• the alkylaluminum compound may be used alone or in combination of two or more kinds.
• alkylaluminum compounds to be charged into the polymerization vessel at the start of the polymerization include trialkylaluminum, dialkylaluminum halides, dialkylaluminum hydrides, and dialkylaluminum alkoxides. Of these, trialkylaluminum is preferred.
• trialkylaluminum examples include trimethylaluminum, triethylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-sec-butylaluminum, and tri-n-octylaluminum. Of these, triisobutylaluminum and trioctylaluminum are preferred.
• dialkylaluminum halides include dimethylaluminum chloride and diisobutylaluminum chloride.
• dialkylaluminum hydride is diisobutylaluminum hydride.
• dialkylaluminum alkoxide is dimethylaluminum methoxide.
• the alkylaluminum compound charged into the polymerization vessel at the start of the polymerization is preferably a long-chain alkylaluminum compound having only alkyl groups having 6 or more carbon atoms.
• Long chain alkylaluminum compounds work well as scavengers.
• the amount of alkylaluminum compound used in the first polymerization is preferably 10 to 5,000 parts by mass, and more preferably 100 to 1,000 parts by mass, per 100 parts by mass of the total amount of titanocene catalyst used in the first polymerization.
• the alkylaluminum compound may be added to the polymerization vessel in a plurality of portions. However, when the alkylaluminum compound is added during the first polymerization, the alkylaluminum compound is added to the polymerization vessel together with other materials. Typically, when the alkylaluminum compound is added during the first polymerization, the alkylaluminum compound is added to the polymerization vessel together with the monomer.
• the number of times that the alkylaluminum compound is added during the first polymerization is not particularly limited, but is preferably 1 to 5 times, more preferably 1 to 3 times, and even more preferably 1 or 2 times.
• the amount of the alkylaluminum compound added per portion is preferably TA/N ⁇ 0.5 to TA/N ⁇ 1.5, more preferably TA/N ⁇ 0.7 to TA/N ⁇ 1.3, and even more preferably TA/N ⁇ 0.9 to TA/N ⁇ 1.1, where TA is the total number of moles of the alkylaluminum compound added in the first polymerization and N is the number of portions.
• the timing of addition of the alkylaluminum compound may be the same as or different from the timing of addition of the monomers, and is preferably the same as the timing of addition of the monomers.
• the first polymerization is carried out in the presence of a titanocene catalyst, an alkylaluminum compound, and a borate compound.
• a titanocene catalyst an alkylaluminum compound
• a borate compound any borate compound that has been used as a cocatalyst in the homopolymerization or copolymerization of a cyclic olefin monomer can be used without any particular limitation.
• the borate compound may be used alone or in combination of two or more kinds.
• preferred borate compounds include triphenylmethylium tetrakis(pentafluorophenyl)borate, dimethylphenylammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, and N-methyldinordecylammonium tetrakis(pentafluorophenyl)borate.
• the amount of the borate compound used in the first polymerization is not particularly limited as long as the addition polymerization reaction proceeds smoothly and a cyclic olefin copolymer having the desired properties is obtained.
• the amount of the borate compound used is preferably 250 to 750 parts by mass, and more preferably 350 to 500 parts by mass, per 100 parts by mass of the total amount of the titanocene catalyst used in the production of the cyclic olefin copolymer.
• the borate compound may be added to the polymerization vessel after the initiation of the first polymerization, other than at the initiation of the first polymerization. However, it is preferred that the entire amount of the borate compound used to produce the cyclic olefin copolymer is charged to the polymerization vessel at the initiation of the first polymerization.
• the polymerization of the above-mentioned monomers may be carried out in the presence of other components than the alkylaluminum compound and the borate compound, as long as the object of the present invention is not impaired.
• a suitable example of the other component is a hindered phenol.
• the hindered phenol any hindered phenol that has been conventionally used as a co-catalyst in homopolymerization or copolymerization of a cyclic olefin monomer can be used without any particular limitation.
• the hindered phenol is a phenol having a bulky substituent at least on one of the two adjacent positions of the phenolic hydroxyl group.
• Examples of the bulky substituent include alkyl groups other than methyl groups such as isopropyl, isobutyl, sec-butyl, and tert-butyl, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, alkoxy groups, aryloxy groups, substituted amino groups, alkylthio groups, and arylthio groups.
• hindered phenol examples include 2,6-di-tert-butyl-4-hydroxytoluene (BHT), 2,6-di-tert-butylphenol, 2-tert-butylphenol, 2-tert-butyl-p-cresol, 3,3',5,5'-tetra-tert-butyl-4,4'-dihydroxybiphenyl, and 3,3',5,5'-tetra-tert-butyl-2,2'-dihydroxybiphenyl.
• BHT 2,6-di-tert-butyl-4-hydroxytoluene
• BHT 2,6-di-tert-butyl-4-hydroxytoluene
• BHT 2,6-di-tert-butyl-4-hydroxytoluene
• BHT 2,6-di-tert-butyl-4-hydroxytoluene
• BHT 2,6-di-tert-butyl-4-hydroxytoluene
• 2,6-di-tert-butylphenol are preferred because they have a small molecular weight and the desired effect of using the hindered phenol can be easily obtained by using a small amount of the hindered phenol.
• the amount of the hindered phenol used in the first polymerization is not particularly limited as long as the addition polymerization reaction proceeds well and a cyclic olefin copolymer having desired properties is obtained.
• the amount of the hindered phenol used is preferably 1 to 1000 parts by mass, more preferably 10 to 500 parts by mass, and even more preferably 100 to 200 parts by mass, relative to 100 parts by mass of the total amount of the titanocene catalyst used in the production of the cyclic olefin copolymer.
• the relationship between the amount of hindered phenol used and the amount of alkylaluminum used is not particularly limited as long as the desired effect is not impaired.
• the amount of hindered phenol used is preferably such that the amount of phenolic hydroxyl groups in the hindered phenol is 1.5 mol or less per mole of alkylaluminum compound.
• the amount of phenolic hydroxyl groups in the hindered phenol is more preferably 1.4 mol or less, even more preferably 1.3 mol or less, and particularly preferably 1.2 mol or less per mole of alkylaluminum compound.
• the first polymerization may be carried out in the presence of a solvent.
• the first polymerization is typically carried out in the presence of a solvent.
• the solvent is not particularly limited as long as it does not inhibit the polymerization reaction.
• Preferred solvents include, for example, hydrocarbon solvents and halogenated hydrocarbon solvents, and hydrocarbon solvents are preferred because of their excellent handling properties, thermal stability, and chemical stability.
• preferred solvents include hydrocarbon solvents such as pentane, hexane, heptane, octane, isooctane, isododecane, mineral oil, cyclohexane, methylcyclohexane, decahydronaphthalene (decalin), benzene, toluene, and xylene, and halogenated hydrocarbon solvents such as chloroform, methylene chloride, dichloromethane, dichloroethane, and chlorobenzene.
• hydrocarbon solvents such as pentane, hexane, heptane, octane, isooctane, isododecane, mineral oil, cyclohexane, methylcyclohexane, decahydronaphthalene (decalin), benzene, toluene, and xylene
• halogenated hydrocarbon solvents such as chloroform,
• the solvent may be charged into the polymerization vessel alone, or may be charged into the polymerization vessel in the form of a monomer solution, a catalyst solution, or a cocatalyst solution.
• the amount of the solvent used is not particularly limited.
• the amount of the solvent used is preferably 100 to 100,000 parts by mass, more preferably 500 to 10,000 parts by mass, and even more preferably 1,000 parts by mass or more and 5,000 parts by mass or less, relative to 100 parts by mass of the total amount of the monomers used in the first polymerization.
• the polymerization temperature in the first polymerization is not particularly limited.
• the polymerization temperature is, for example, preferably ⁇ 20 to 200° C., more preferably ⁇ 10 to 10° C., and further preferably ⁇ 5 to 5° C.
• the time for the first polymerization is not particularly limited as long as the polymerization proceeds until a predetermined amount of the monomer is consumed.
• polymerization of the monomer is carried out until the reaction rate of the cyclic olefin monomer becomes 80 mol % or more based on the total number of moles of the cyclic olefin monomer added into the polymerization vessel at the start of the first polymerization and during the first polymerization.
• the time for the first polymerization is, for example, preferably 5 to 30 minutes, more preferably 8 to 20 minutes, and even more preferably 10 to 15 minutes.
• the monomer may be added to the polymerization vessel in several portions.
• the reaction rate of the cyclic olefin monomer is 80 mol% or more with respect to the total number of moles of the cyclic olefin monomer added into the polymerization vessel at the start of the first polymerization and during the first polymerization, the reaction rate of the cyclic olefin monomer from the start of the first polymerization to before the second monomer addition in the first polymerization, the reaction rate of the cyclic olefin monomer from the mth monomer addition to the (m+1)th monomer addition, and the reaction rate of the cyclic olefin monomer from the last monomer addition to the end of the first polymerization are not particularly limited, and are preferably 80 mol% or
• m is any integer equal to or greater than 1.
• the reaction rate of the cyclic olefin monomer relative to the total number of moles of the cyclic olefin monomer added into the polymerization vessel at the start of the first polymerization and during the first polymerization can be calculated by measuring the amount of the cyclic olefin monomer remaining in the polymerization vessel at the end of the first polymerization.
• the reaction rate of the cyclic olefin monomer from the start of the first polymerization to before the second monomer addition in the first polymerization is determined based on the number of moles of the cyclic olefin monomer charged into the polymerization vessel before the start of the first polymerization.
• the reaction rate of the cyclic olefin monomer from the mth monomer addition to the m+1th monomer addition is determined based on the number of moles of the cyclic olefin monomer in the polymerization vessel immediately after the mth monomer addition.
• the number of moles of the cyclic olefin monomer in the polymerization vessel immediately after the mth monomer addition is the sum of the number of moles of the cyclic olefin monomer in the polymerization vessel immediately before the mth monomer addition and the number of moles of the cyclic olefin monomer added to the polymerization vessel by the mth monomer addition.
• the reaction rate of the cyclic olefin monomer from the addition of the last monomer to the end of the first polymerization is determined based on the number of moles of the cyclic olefin monomer in the polymerization vessel immediately after the addition of the last monomer.
• the number of moles of the cyclic olefin monomer in the polymerization vessel immediately after the addition of the last monomer is the sum of the number of moles of the cyclic olefin monomer in the polymerization vessel immediately before the addition of the last monomer and the number of moles of the cyclic olefin monomer added to the polymerization vessel by the addition of the last monomer.
• the atmosphere in which the first polymerization reaction is carried out is not particularly limited, but an inert gas atmosphere is preferable. Nitrogen gas or helium gas can be used as the inert gas.
• the titanocene catalyst, the alkylaluminum compound, the borate compound, the other components, and the monomer may each be added to the polymerization vessel in two or more separate additions.
• the polymerization of the monomer is always initiated in the presence of the titanocene catalyst, the alkylaluminum compound, and the borate compound.
• the alkylaluminum compound is added alone to the polymerization vessel after the first polymerization step, although it is permissible to add a component inert to the polymerization reaction, such as an organic solvent, together with the alkylaluminum compound after the first polymerization step.
• a component inert such as an organic solvent
• the addition of an alkylaluminum compound together with a component active in the polymerization reaction, such as a monomer, a catalyst, or a cocatalyst does not fall under the category of the addition of an alkylaluminum compound alone after the first polymerization.
• the alkylaluminum compound added to the polymerization vessel after the first polymerization acts as a chain transfer agent.
• the yield of the cyclic olefin copolymer per unit weight of the titanocene catalyst can be increased without excessively increasing the dispersity ratio of the molecular weight of the resulting cyclic olefin copolymer.
• the same compound as the alkylaluminum compound used in the first polymerization can be used.
• the alkylaluminum compound added to the polymerization vessel after the first polymerization may be the same or different from the alkylaluminum compound used in the first polymerization.
• the alkylaluminum compound to be added to the polymerization vessel after the first polymerization may be used alone or in combination of two or more kinds.
• suitable trialkylaluminum to be added to the polymerization vessel after the first polymerization include trimethylaluminum, triethylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-sec-butylaluminum, and tri-n-octylaluminum. Of these, trimethylaluminum and triethylaluminum are preferred.
• the alkylaluminum compound added to the polymerization vessel after the first polymerization is preferably a short-chain alkylaluminum compound having only alkyl groups having 5 or less carbon atoms.
• the short-chain alkylaluminum compound acts well as a chain transfer agent, and therefore, when the short-chain alkylaluminum compound is used as the alkylaluminum compound added to the polymerization vessel after the first polymerization, a cyclic olefin copolymer having particularly excellent heat resistance and toughness is easily obtained, and the yield of the cyclic olefin copolymer per unit weight of the titanocene catalyst is easily increased.
• the purpose of use of the alkylaluminum compound charged into the reaction vessel at the start of the first polymerization is different from the purpose of use of the alkylaluminum compound added into the polymerization vessel after the first polymerization.
• the second polymerization may be repeatedly carried out a plurality of times.
• the "end of the second polymerization" in the above "from the start of the first polymerization to the end of the second polymerization” refers to the end of the last second polymerization.
• the alkylaluminum compound I and the alkylaluminum compound II may each be added to the polymerization vessel at any timing from the start of the first polymerization to the end of the final second polymerization.
• Alkyl aluminum compound I has at least one alkyl group having at least 6 carbon atoms.
• Alkyl aluminum compound II has at least one alkyl group having at most 5 carbon atoms.
• alkylaluminum compound I may be added to the polymerization vessel at the start of the first polymerization, and alkylaluminum compound II may be added to the polymerization vessel at any time after the first polymerization.
• alkylaluminum compound II may be added to the polymerization vessel at the start of the first polymerization, and alkylaluminum compound I may be added to the polymerization vessel at any time after the first polymerization.
• the alkylaluminum compound I and the alkylaluminum compound II may be added simultaneously to the polymerization vessel, or a mixture of the alkylaluminum compound I and the alkylaluminum compound II may be added to the polymerization vessel.
• any alkylaluminum compound may be added to the polymerization vessel at any time after the first polymerization, and it is preferable to add the alkylaluminum compound II to the polymerization vessel at any time after the first polymerization.
• Alkyl aluminum compound I has at least one alkyl group having at least 6 carbon atoms.
• Alkyl aluminum compound II has at least one alkyl group having at most 5 carbon atoms.
• the alkylaluminum compound I preferably has two or three alkyl groups having 6 or more carbon atoms, more preferably three alkyl groups having 6 or more carbon atoms.
• the alkylaluminum compound II has two or three alkyl groups containing up to 5 carbon atoms, more preferably three alkyl groups containing up to 5 carbon atoms.
• the alkylaluminum compound I and the alkylaluminum compound II may each be a dialkylaluminum halide, a dialkylaluminum hydride, or a dialkylaluminum alkoxide.
• alkylaluminum compound I when two types of alkylaluminum compounds having an alkyl group with 6 or more carbon atoms and an alkyl group with 5 or less carbon atoms are used as the alkylaluminum compound, either of the alkylaluminum compounds may be alkylaluminum compound I, and either of the alkylaluminum compounds may be alkylaluminum compound II.
• the molar ratio of alkylaluminum compound I to alkylaluminum compound II is preferably 2:8 to 8:2, more preferably 3:7 to 7:3, and even more preferably 4:6 to 6:4.
• the addition of the alkylaluminum compound after the first polymerization and the second polymerization may be repeated.
• the alkylaluminum compound may be added to the polymerization vessel multiple times.
• the total amount of the alkylaluminum compounds added to the polymerization vessel after the first polymerization is preferably 1 to 1,000 parts by mass, and more preferably 10 to 100 parts by mass, relative to 100 parts by mass of the total amount of the titanocene catalyst used in the production of the cyclic olefin copolymer.
• the amount of the alkylaluminum compound added per time is preferably TA/N ⁇ 0.5 to TA/N ⁇ 1.5, more preferably TA/N ⁇ 0.7 to TA/N ⁇ 1.3, and even more preferably TA/N ⁇ 0.9 to TA/N ⁇ 1.1, where TA is the total mole number of the alkylaluminum compound added after the first polymerization and N is the number of divisions.
• ⁇ Second Polymerization> After the first polymerization, an alkylaluminum compound is added, and then monomers are added to the polymerization vessel, followed by polymerization of the monomers in a second polymerization step.
• the composition of the monomers added to the polymerization vessel may be the same as or different from the composition of the monomers in the first polymerization, and is preferably the same as the composition of the monomers in the first polymerization.
• a cyclic olefin monomer or only an ⁇ -olefin may be added as a monomer, but it is preferable to add a cyclic olefin monomer and a monomer containing an ⁇ -olefin.
• the addition of the alkylaluminum compound and the second polymerization carried out after the first polymerization may be carried out repeatedly.
• the second polymerization may be carried out multiple times after the first polymerization.
• the total amount of monomers added to the polymerization vessel in the second polymerization is preferably 20 to 80 mol%, more preferably 30 to 70 mol%, and even more preferably 40 to 60 mol%, based on the total number of moles of monomers used to produce the cyclic olefin copolymer.
• the monomer may be added in multiple batches.
• the amount of monomer added per batch is preferably TA/N x 0.5 to TA/N x 1.5, more preferably TA/N x 0.7 to TA/N x 1.3, and even more preferably TA/N x 0.9 to TA/N x 1.1, where TA is the total number of moles of monomer added in one second polymerization and N is the number of divisions.
• the alkylaluminum compound acts as a scavenger that captures water, oxygen, and other impurities in the monomer.
• the amount of the alkylaluminum compound added together with the monomers is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 1 part by mass, based on 100 parts by mass of the total amount of the monomers used in the second polymerization.
• the reaction temperature is the same as that in the first polymerization.
• the reaction time is not particularly limited.
• the second polymerization may be continued until a desired amount of a cyclic olefin copolymer having desired physical properties is produced.
• the time for the second polymerization is, for example, preferably from 5 to 300 minutes, more preferably from 8 to 120 minutes, and even more preferably from 10 to 60 minutes.
• the polymerization time of the second polymerization is the total polymerization time of the plurality of second polymerizations.
• the polymerization time in each of the plurality of second polymerizations is not particularly limited.
• the time of each second polymerization is preferably TT/N ⁇ 0.5 to TT/N ⁇ 1.5, more preferably TT/N ⁇ 0.7 to TT/N ⁇ 1.3, and even more preferably TT/N ⁇ 0.9 to TT/N ⁇ 1.1, where TT is the total time of the multiple second polymerizations and N is the number of times the second polymerization is carried out.
• the polymerization reaction may be terminated after the first polymerization, the addition of the alkylaluminum compound after the first polymerization, and the second polymerization.
• the number of steps is small, and the cyclic olefin copolymer can be easily produced.
• the monomer may be added in two or more portions in the first polymerization and/or the second polymerization, and it is more preferable to add the monomer in two portions in the first polymerization and/or the second polymerization. It is preferable to add the monomer in two portions in both the first polymerization and the second polymerization.
• the reaction rate of the cyclic olefin monomer in the second polymerization is not particularly limited, but is preferably 80 mol % or more based on the total number of moles of the cyclic olefin monomer added to the polymerization vessel at the start of the second polymerization and during the second polymerization.
• the monomers may be added to the polymerization vessel in multiple portions.
• the reaction rate of the cyclic olefin monomer from the start of the second polymerization to before the second monomer addition in the second polymerization, the reaction rate of the cyclic olefin monomer from the mth monomer addition to the (m+1)th monomer addition, and the reaction rate of the cyclic olefin monomer from the last monomer addition to the end of the second polymerization are not particularly limited, and are preferably 80 mol% or more.
• m is any integer equal to or greater than 1.
• the reaction rate of the cyclic olefin monomer from the start of the second polymerization to before the second monomer addition in the second polymerization is determined based on the number of moles of the cyclic olefin monomer present in the polymerization vessel when the second polymerization is started.
• the number of moles of the cyclic olefin monomer present in the polymerization vessel when the second polymerization is started is the sum of the number of moles of the cyclic olefin monomer remaining in the polymerization vessel after the first polymerization and the number of moles of the cyclic olefin monomer added to the polymerization vessel after the addition of the alkylaluminum compound and before the start of the second polymerization.
• the reaction rate of the cyclic olefin monomer from the mth monomer addition to the m+1th monomer addition is determined based on the number of moles of the cyclic olefin monomer in the polymerization vessel immediately after the mth monomer addition.
• the number of moles of the cyclic olefin monomer in the polymerization vessel immediately after the mth monomer addition is the sum of the number of moles of the cyclic olefin monomer in the polymerization vessel immediately before the mth monomer addition and the number of moles of the cyclic olefin monomer added to the polymerization vessel by the mth monomer addition.
• the reaction rate of the cyclic olefin monomer from the addition of the last monomer to the end of the second polymerization is determined based on the number of moles of the cyclic olefin monomer in the polymerization vessel immediately after the addition of the last monomer.
• the number of moles of the cyclic olefin monomer in the polymerization vessel immediately after the addition of the last monomer is the sum of the number of moles of the cyclic olefin monomer in the polymerization vessel immediately before the addition of the last monomer and the number of moles of the cyclic olefin monomer added to the polymerization vessel by the addition of the last monomer.
• the addition of the alkylaluminum compound and the secondary polymerization may be repeated until the number of alkylaluminum compound additions reaches n.
• the pth addition of alkylaluminum among the 2nd to nth additions is performed after the (p-1)th secondary polymerization, where n is an integer of 2 or more and p is an integer of 2 or more and n or less.
• the p-th addition of alkylaluminum is carried out after the reaction rate of the cyclic olefin monomer in the (p-1)th second polymerization becomes 80 mol % or more based on the total number of moles of the cyclic olefin monomer in the polymerization vessel at the start of the (p-1)th second polymerization and the number of moles of the cyclic olefin monomer added to the polymerization vessel during the (p-1)th second polymerization.
• the monomer may be added to the polymerization vessel in two or more portions.
• a cyclic olefin monomer may be added to the polymerization vessel during the second polymerization.
• the number of moles of the cyclic olefin monomer in the polymerization vessel at the start of the (p-1)th second polymerization is the sum of the number of moles of the cyclic olefin monomer remaining in the polymerization vessel at the end of the (p-2)th second polymerization and the number of moles of the cyclic olefin monomer added to the polymerization vessel immediately before the start of the (p-1)th second polymerization.
• the reaction rate of the cyclic olefin monomer in the final second polymerization does not have to be 80 mol % or more based on the total amount of the cyclic olefin monomer added to the polymerization vessel at the start of the final second polymerization and during the final second polymerization.
• the polymerization reaction is terminated after the nth second polymerization.
• the monomer in at least one of the first polymerization and/or n number of second polymerizations, may be divided into two or more portions and added in portions to the polymerization vessel, and it is preferable that in at least one of the first polymerization and/or n number of second polymerizations, the monomer is divided into two portions and added in portions to the polymerization vessel. It is preferable that in all of the first polymerization and n number of second polymerizations, the monomer is divided into two portions and added in portions to the polymerization vessel.
• the amount of the cyclic olefin copolymer obtained is 200 g or more per 1 g of titanocene catalyst, and that the number average molecular weight of the cyclic olefin copolymer obtained is 10,000 to 100,000.
• a titanocene catalyst having the following structure was used: In the following formula, Me is a methyl group, and t-Bu is a tert-butyl group.
• Example 1 In Example 1, 2-norbornene (Nb) and 1-octene (Oct) were used in the ratios shown in Table 1, such that the total amount of 2-norbornene and 1-octene was 17.28 mmol.
• Second Polymerization 2-norbornene, 1/4 amount of 1-octene, and 0.160 mmol of tri-n-octyl aluminum were added to a Schlenk flask with a capacity of 50 mL and replaced with a nitrogen atmosphere. The contents of the flask were then diluted to a volume of 21.9 mL using decalin. The contents of the flask were then cooled to 0°C.
• a toluene solution with a titanocene catalyst concentration of 0.16 mmol/mL was added to the reaction solution so that the amount of the titanocene catalyst was 0.016 mmol.
• a toluene solution with a borate compound concentration of 0.008 mmol/L was added to the reaction solution so that the amount of the borate compound was 0.016 mmol.
• Triphenylmethylium tetrakis(pentafluorophenyl)borate was used as the borate compound.
• the reaction rate of 2-norbornene was 95 mol % based on the number of moles of 2-norbornene at the start of polymerization. After 5 minutes of reaction, 2-norbornene, 1 ⁇ 4 of the amount of 1-octene, and 0.016 mmol of tri-n-octylaluminum were added to the Schlenk flask, and the addition polymerization reaction was continued for 5 minutes. After 5 minutes of reaction following the addition of the monomer, the reaction rate of 2-norbornene was 99 mol % based on the number of moles of 2-norbornene at the time of the addition of the monomer.
• Example 2 A cyclic olefin copolymer was obtained in the same manner as in Example 1, except that tri-n-octylaluminum used in the first polymerization and the second polymerization was replaced with triisobutylaluminum.
• the charging ratio of norbornene and 1-octene was as shown in Table 1.
• Table 2 shows the monomer reaction rates from the start of polymerization to the addition of monomers and the reaction rate of 2-norbornene from the addition of monomers to the end of polymerization in the first and second polymerizations.
• Example 3 A cyclic olefin copolymer was obtained in the same manner as in Example 1, except that the triethylaluminum added after the first polymerization was changed to trimethylaluminum.
• the charging ratio of norbornene and 1-octene was as shown in Table 1.
• Table 2 shows the reaction rate of 2-norbornene from the start of polymerization to the addition of monomers and the reaction rate of 2-norbornene from the addition of monomers to the end of polymerization in the first and second polymerizations.
• Example 4 A cyclic olefin copolymer was obtained in the same manner as in Example 1, except that tri-n-octylaluminum used in the first and second polymerizations was changed to triisobutylaluminum, and triethylaluminum added after the first polymerization was changed to trimethylaluminum.
• the charging ratio of norbornene and 1-octene was as shown in Table 1.
• Table 2 shows the reaction rate of 2-norbornene from the start of polymerization to the addition of monomers and the reaction rate of 2-norbornene from the addition of monomers to the end of polymerization in the first and second polymerizations.
• Example 5 A cyclic olefin copolymer was obtained in the same manner as in Example 1, except that the tri-n-octylaluminum used in the first polymerization was changed to an equimolar mixture of tri-n-octylaluminum and triethylaluminum.
• the charging ratio of norbornene and 1-octene was as shown in Table 1.
• Table 2 shows the reaction rate of 2-norbornene from the start of polymerization to the addition of monomers and the reaction rate of 2-norbornene from the addition of monomers to the end of polymerization in the first and second polymerizations.
• Example 6 A cyclic olefin copolymer was obtained in the same manner as in Example 1, except that the triethylaluminum added after the first polymerization was changed to an equimolar mixture of tri-n-octylaluminum and triethylaluminum.
• the charging ratio of norbornene and 1-octene was as shown in Table 1.
• Table 2 shows the reaction rate of 2-norbornene from the start of polymerization to the addition of monomers and the reaction rate of 2-norbornene from the addition of monomers to the end of polymerization in the first and second polymerizations.
• Example 7 A cyclic olefin copolymer was obtained in the same manner as in Example 1, except that the tri-n-octylaluminum used in the first polymerization was changed to trimethylaluminum, and the triethylaluminum added after the first polymerization was changed to trimethylaluminum.
• the charging ratio of norbornene and 1-octene was as shown in Table 1.
• Table 2 shows the reaction rate of 2-norbornene from the start of polymerization to the addition of monomers and the reaction rate of 2-norbornene from the addition of monomers to the end of polymerization in the first and second polymerizations.
• Example 8 In Example 8, 2-norbornene (Nb) and 1-octene (Oct) in the ratio shown in Table 1 were used in amounts such that the total amount of 2-norbornene and 1-octene was 17.28 mmol.
• Second Polymerization In a Schlenk flask with a capacity of 50 mL and substituted with a nitrogen atmosphere, 2-norbornene, 1/2 the amount of 1-octene, and 0.160 mmol of tri-n-octyl aluminum were added. Then, the contents of the flask were diluted to a volume of 21.9 mL using decalin. Next, the contents of the flask were cooled to 0°C.
• Example 9 to 16 cyclic olefin copolymers were obtained in the same manner as in Examples 1 to 8, except that 1-octene was replaced with 1-hexene (Hex), respectively. That is, the conditions of Example 1 are the same as those of Example 9 except for the type of monomer. The conditions of Example 2 are the same as those of Example 10 except for the type of monomer. Similarly, the conditions of Examples 3 to 8 are the same as those of Examples 11 to 16 except for the type of monomer.
• CC1 6.5 mass % (as the content of Al atoms) MMAO-3A toluene solution (a solution of methylisobutylaluminoxane represented by [(CH 3 ) 0.7 (iso-C 4 H 9 ) 0.3 AlO] n , manufactured by Tosoh Finechem Co., Ltd., containing 6 mol % of trimethylaluminum based on the total Al).
• CC2 9.0 mass% (as the content of Al atoms) TMAO-211 toluene solution (a solution of methylaluminoxane, manufactured by Tosoh Finechem Co., Ltd., containing 26 mol% trimethylaluminum based on the total Al)
• the molecular weights were measured by gel permeation chromatography and the glass transition temperatures were measured by the above-mentioned method. The results are shown in Table 3. If the material has at least one glass transition temperature in the range below 0° C., in the range of 0 to 100° C., and in the range of 160 to 300° C., it can be said to have excellent toughness. In addition, when the material has at least one glass transition temperature in the range of less than 0 ° C., in the range of 0 to 100 ° C., and in the range of 160 to 300 ° C., the material has excellent toughness. As shown in the examples of JP-A No. 2022-030194.
• the films used as samples in the measurement of the glass transition temperature were prepared in the following manner.
• a Kapton® film measuring 10 cm x 10 cm x 50 ⁇ m was used to prepare a mold with a depth of 50 ⁇ m.
• the cyclic olefin copolymer filled in the mold was vacuum-pressed using a hot vacuum press under conditions of a pressure of 15 MPa, a temperature of 320 to 340°C, and a time of 15 minutes. After pressing, the pressed cyclic olefin copolymer was sandwiched between metal plates at room temperature to rapidly cool it. After cooling, the metal plates were removed to obtain a cyclic olefin copolymer film with a thickness of about 50 ⁇ m.
• the cyclic olefin copolymer has glass transition temperatures in the range of less than 0° C., in the range of 0 to 100° C., and in the range of 160 to 300° C., respectively, and has excellent toughness, and can be efficiently produced.
• Comparative Example 1 in which the first polymerization and the second polymerization were performed but no alkylaluminum compound was added after the first polymerization, Comparative Example 2 in which the polymerization was performed in one stage, and Comparative Example 3 in which the reaction rate of the cyclic olefin monomer in the first polymerization was less than 80 mol%, it was not possible to achieve both the toughness of the resulting cyclic olefin copolymer and good production efficiency of the cyclic olefin copolymer.

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